Metal-doped cobalt precursor for preparing positive electrode active material for secondary battery

ABSTRACT

Provided is a cobalt precursor for preparing a lithium cobalt oxide of a layered structure which is included in a positive electrode active material, wherein the cobalt precursor is cobalt oxyhydroxide (CoM′OOH) doped with, as dopants, magnesium (Mg) and M′ different from the magnesium.

CROSS-REFERENCE TO RELATED APPLICATION

The present application is based on, and claims priority from, KoreanPatent Application No. 10-2016-0175222, filed on Dec. 21, 2016, thedisclosure of which is hereby incorporated by reference herein in itsentirety.

The present invention relates to a metal-doped cobalt precursor forpreparing a positive electrode active material for a secondary battery.

TECHNICAL FIELD Background Art

In recent years, a demand for environment-friendly alternative energysources has become an indispensable factor for the future, as the priceincrease of energy sources due to depletion of fossil fuels and theinterest in environmental pollution are amplified. For this reason, avariety of electric power generation technologies such as nuclear power,solar power, wind power, tidal power, etc. have been continuouslystudied, and energy storage devices for more efficient use of generatedenergy have also been attracting much attention.

Particularly, as technology development and demands for mobile devicesincrease, demands for batteries as energy sources are rapidlyincreasing. Recently, use of a secondary battery as a power source foran electric vehicle (EV), a hybrid electric vehicle (HEV), etc. has beenrealized, and its application field has also been expanded to use as anauxiliary power source through a grid. Therefore, many researches onbatteries meeting diverse demands have been conducted.

In terms of the shape of the battery, there are high demands for aprismatic type secondary battery and a pouch type secondary batterywhich have a thin thickness to be applicable in products such as acellular phone, etc. In terms of materials, there are high demands forlithium secondary batteries such as a lithium ion battery and a lithiumion polymer battery which have advantages of high energy density,discharge voltage, and output power stability.

As a positive electrode material for the lithium secondary battery,LiCoO₂, a ternary system material (NMC/NCA), LiMnO₄, LiFePO₄, etc. iscurrently used. Of them, LiCoO₂ has problems in that cobalt is expensiveand LiCoO₂ has low capacity at the same voltage, as compared withternary system materials. Therefore, use of ternary system materials isgradually increasing in order to increase the capacity of secondarybatteries.

However, LiCoO₂ has been widely used until now, because it hasadvantages of high rolling density, etc. To develop high-capacitysecondary batteries, studies are conducted to increase an operatingvoltage.

In general, lithium cobalt oxide, for example, LiCoO₂ has an R-3mrhombohedral layered structure. In detail, the lithium cobalt oxide hasa structure in which lithium, cobalt, and oxygen are regularly arrangedin the form of O—Li—O—Co—O—Li—O—Co—O along a [111] crystal face of arock salt structure and such a structure is also referred to as anO3-type layered structure.

In this regard, when the lithium cobalt oxide is included in a positiveelectrode active material, lithium ions are deintercalated from acrystal lattice of the lithium cobalt oxide when a lithium secondarybattery including the positive active material is charged. Inparticular, as the charging voltage, specifically, the charging cutoffvoltage is higher, the amount of lithium ions deintercalated from thecrystal lattice of the lithium cobalt oxide increases. Accordingly, at ahigher charging cut-off voltage, the layered structure of lithium cobaltoxide is more likely to undergo a phase transition due to changes in thecrystal lattice structure.

More specifically, LiCoO₂ may maintain the O3-type layered structure (O3phase) up to a charging voltage of 4.53 V based on lithium aftercharging is completed. However, when the charging voltage exceeds 4.53V, the amount of lithium ions deintercalated from the crystal lattice ofthe lithium cobalt oxide increases, and as a result, a phase transitionfrom the O3-type layered structure to an O1-type layered structure (O1phase), in which Li is not present in the crystal lattice, may occur.Therefore, when the charging voltage exceeds 4.53 V, a phase transitionfrom the O3-type layered structure to an H1-3-type layered structure(H1-3 phase) may occur, in which the O3-type layered structure and theO1-type layered structure coexist in the crystal lattice.

In this regard, the phase transitions from the O3-type layered structureto the H1-3-type layered structure and from the O3-type layeredstructure to the O1-type layered structure may be partiallyirreversible, and in the H1-3-type layered structure and the O1-typelayered structure, lithium ions capable of beingintercalated/deintercalated may decrease. Thus, when the phasetransition occurs, the operating efficiency and the discharge rate andlifespan characteristics of the lithium battery may deterioratedrastically.

Particularly, according to the nature of lithium cobalt oxide, whenlithium ions are reduced, the oxidation of Co³⁺ ions to Co⁴⁺ ions with alower ionic radius occurs to cause an increase in structural stress, andas a result, the above problems are exacerbated.

Therefore, in order to prevent deterioration of the operating efficiencyand the discharge rate and lifespan characteristics of the lithiumbattery at a high voltage of more than 4.53 V and to improve theperformances, it is necessary to inhibit the phase transition of lithiumcobalt oxide.

Accordingly, there is a high demand for a technology capable offundamentally solve the above problems.

DISCLOSURE Technical Problem

An object of the present invention is to solve the above-describedproblems of the prior art and the technical problems which have beendemanded to be solved.

The present inventors have conducted intensive studies and variousexperiments, and as described below, they found that when a cobaltprecursor is composed of cobalt oxyhydroxide (CoM′OOH) which is dopedwith, as dopants, magnesium (Mg) and M′ different from the magnesium,and the cobalt precursor is used to prepare a positive electrode activematerial, the dopants doped into lithium cobalt oxide exhibit aparticular average oxidation number, and as a result, a crystal latticehaving excellent structural stability may be formed, oxidation of cobaltions due to reduction of lithium ions in lithium cobalt oxide may beprevented to prevent a reduction of ionic radius and an increase instructural stress, and an irreversible phase transition and a structuralchange of the lithium cobalt oxide may be effectively prevented even ata charging voltage of higher than 4.53 V, thereby preventingdeterioration of operating efficiency and discharge rate and lifespancharacteristics of a secondary battery including the positive electrodeactive material and improving performances thereof, leading to thepresent invention.

Technical Solution

To achieve the above object, a cobalt precursor for preparing a positiveelectrode active material according to the present invention may be acobalt precursor for preparing a lithium cobalt oxide of a layeredstructure which is included in the positive electrode active material,wherein the cobalt precursor may be cobalt oxyhydroxide((Co_(x)Mg_(y)M′_(z))OOH) (wherein x, y, and z satisfy the followingweight ratio conditions: a content of x is in the range of 99 wt % to99.8 wt % and a total content of y and z is in the range of 0.2 wt % to1 wt %, when the sum of x, y, and z is regarded as 100 wt %; M′ is oneor more selected from the group consisting of Al, Ti, Mn, Zr, Ba, B, Ca,Ta, Mo, Nb, W, Sr and PO₄) which is doped with, as dopants, magnesium(Mg) and M′ different from the magnesium.

Here, y and z are each essentially included in the range of more than 0wt %. In other words, y and z may satisfy the following conditions: yand z may be each included in the range of more than 0 wt % and lessthan 1 wt %, specifically, 0.01 wt % to 0.99 wt %, and at the same time,the total content of y and z may be 0.2 wt % to 1 wt %. Hereinbelow, thecontents of y and z are the same as described above.

The lithium cobalt oxide prepared using the precursor may be representedby the following Formula 1, wherein the precursor is doped with, asdopants, magnesium (Mg) and M′ different from the magnesium; and

the dopants have an average oxidation number of more than +2 to +2.5 orless in the lithium cobalt oxide:

Li_(a)(Co_(x)Mg_(y)M′_(z))O₂   (1)

wherein a satisfies 0.95≤a≤1.05;

x, y, and z satisfy the following weight ratio conditions: a content ofx is in the range of 99 wt % to 99.8 wt % and a total content of y and zis in the range of 0.2 wt % to 1 wt %, when the sum of x, y, and z isregarded as 100 wt %; and

M′ is one or more selected from the group consisting of Al, Ti, Mn, Zr,Ba, B, Ca, Ta, Mo, Nb, W, Sr, and PO₄.

Accordingly, the dopants having a particular oxidation number may bedoped and placed at the cobalt position of a crystal lattice of lithiumcobalt oxide, and therefore, the crystal lattice having excellentstructural stability may be formed, oxidation of cobalt ions due toreduction of lithium ions in lithium cobalt oxide may be prevented toprevent a reduction of ionic radius and an increase in structuralstress, and an irreversible phase transition and a structural change ofthe lithium cobalt oxide may be effectively prevented even at a chargingvoltage of higher than 4.53 V, thereby preventing deterioration ofoperating efficiency and discharge rate and lifespan characteristics ofa secondary battery including the positive electrode active material andimproving performances thereof.

When the average oxidation number of the dopants is +2 or less or morethan +2.5 out of the above range, the ionic radius of the dopants ischanged or the dopants do not have the average oxidation numbercorresponding to cobalt, and thus the dopants may not be easily dopedand placed at the cobalt position of the crystal lattice of the lithiumcobalt oxide. As a result, it is difficult to obtain the effects ofpreventing the irreversible phase transition and structural change ofthe lithium cobalt oxide and oxidation of cobalt ions due to the dopantshaving the particular average oxidation number.

Here, the average oxidation number may be determined by Equation of“[oxidation number of magnesium*number of mole of magnesium+oxidationnumber of M′*number of mole of M′]/number of mole of magnesium+number ofmole of M′”.

In this regard, instead of doping the cobalt precursor with the dopants,if a lithium precursor and the cobalt precursor are doped with thedopants at the same time while being reacted with each other duringpreparation of lithium cobalt oxide, there is a possibility ofcompetition between the dopants and the lithium ions while the dopantsare doped and placed at the cobalt position of the crystal lattice ofthe lithium cobalt oxide. In this case, doping of the cobalt positionwith the dopants may not be easy.

Particularly, when the lithium precursor and the cobalt precursor aredoped with the dopants at the same time while being reacted with eachother during preparation of lithium cobalt oxide, at least three processconditions, such as respective contents of the lithium precursor, thecobalt precursor, and the dopants, must be considered in order tocontrol the average oxidation number of the dopants.

However, when the cobalt precursor is preferentially doped with thedopants, only two process conditions, such as respective contents of thedopants and the cobalt precursor, need to be considered during thedoping process. In addition, when the dopant-doped cobalt precursor isreacted with the lithium precursor to prepare lithium cobalt oxide, onlytwo process conditions, such as respective contents of the cobaltprecursor and the lithium precursor, need to be considered. Therefore,the number of variables to be considered in a single process step isreduced, which may facilitate the design of the process conditions andmay effectively reduce a defect rate of a product.

Further, when the dopants are doped into the final lithium cobalt oxide,rather than the cobalt precursor at the precursor stage, doping of thecobalt position with the dopants may not be easy because of the crystallattice structure already formed during the preparation of lithiumcobalt oxide.

Meanwhile, the dopants may be magnesium (Mg) and (M′) which is,different from the magnesium, one or more selected from the groupconsisting of Al, Ti, Mn, Zr, Ba, B, Ca, Ta, Mo, Nb, W, Sr and PO₄,wherein the magnesium may have the oxidation number of +2 and the other(M′) excluding the magnesium may have the oxidation number of +2 or +3,and consequently, the average oxidation number of the dopants may beeasily controlled in the range of more than +2 and +2.5 or less.Accordingly, the dopants may be controlled to have a similar ionicradius to that of the cobalt ion, and thus the dopants may have theaverage oxidation number corresponding to cobalt. As a result, thedopants may be appropriately doped and placed at the cobalt position ofthe crystal lattice of the cobalt precursor for the preparation of thelithium cobalt oxide.

In a specific embodiment, the lithium cobalt oxide may have a structure,in which the crystal structure is maintained in a charging range of morethan 4.5 V and 4.8 V or less.

In this regard, the crystal structure may have O3 phase.

As described above, when a known lithium cobalt oxide is included in thepositive electrode active material, the lithium cobalt oxide maymaintain the O3-type layered structure (O3 phase) up to a chargingvoltage of 4.53 V after charging is completed. However, when thecharging voltage is more than 4.52 V, the amount of lithium ionsdeintercalated from the crystal lattice of the lithium cobalt oxideincreases, and as a result, a phase transition from the O3-type layeredstructure to an H1-3-type layered structure (H1-3 phase) may occur.According to the nature of lithium cobalt oxide, as lithium ions arereduced, the oxidation of Co³⁺ ions to Co⁴⁺ ions with a lower ionicradius occurs to cause an increase in structural stress, and as aresult, the above problems are exacerbated. Ultimately, the operatingefficiency and the discharge rate and lifespan characteristics of alithium battery may be deteriorated drastically.

In contrast, when lithium cobalt oxide is prepared using the cobaltprecursor according to the present invention, the dopants may beappropriately doped and placed at the cobalt position of the crystallattice of the lithium cobalt oxide, because the dopants may have theaverage oxidation number of the particular range, and may be controlledto have a similar ionic radius to that of the cobalt ion, and thus thedopants may have the average oxidation number corresponding to cobalt.As a result, oxidation of the cobalt ions in the lithium cobalt oxidemay be prevented and its structural stability may be improved, andtherefore, the lithium cobalt oxide may maintain the crystal structureof O3 phase in a charging range of more than 4.5 V and 4.8 V or less,thereby effectively preventing deterioration of operating efficiency andthe discharge rate and lifespan characteristics of a lithium battery.

Further, the lithium cobalt oxide may have no plateau at 4.55 V ofinitial charge/discharge profiles.

More specifically, a general lithium cobalt oxide may not maintain thecrystal structure of O3 phase at 4.55 V of initial charge/dischargeprofiles and may undergo a phase transition to H1-3 phase. Thus, due totwo phase reaction, a plateau occurs, in which the voltage of thebattery maintains constant.

In contrast, the lithium cobalt oxide prepared by using the cobaltprecursor according to the present invention may maintain the stablecrystal structure of O3 phase, may not undergo two phase reaction, andmay maintain a stable charge/discharge state, and accordingly, thelithium cobalt oxide may not have a plateau, in which the voltage of thebattery maintains constant, at 4.55 V of initial charge/dischargeprofiles.

Meanwhile, the positive electrode active material may be in the form ofparticles, and the surface of the particle may be coated with Al₂O₃.

Generally, when a high voltage of to 4.5 V or more is applied to lithiumcobalt oxide, there are problems in that Li usage of LiCoO₂ is increasedto make the surface unstable, and side reactions with an electrolyteoccur to generate gas, resulting in a reduction of safety such as aswelling phenomenon, etc., an increase of possibility of structuralinstability, and a rapid reduction of lifespan characteristics.

For this reason, when the positive electrode active material includingthe lithium cobalt oxide prepared using the cobalt oxide according tothe present invention is coated with Al₂ 0 ₃ on the particle surfacethereof, reactivity of the particle surface of the positive electrodeactive material with respect to an electrolyte may be inhibited,side-reactions caused thereby may suppressed, and safety and lifespancharacteristics may be further improved.

In this regard, the Al₂O₃ may be applied at a thickness of 0.2% to 5%,based on a diameter of the positive electrode active material particle.

When the coating thickness of Al₂O₃ is too thin out of the above range,it is difficult to achieve the desired effects. On the contrary, whenthe coating thickness of Al₂O₃ is too thick out of the above range, thecapacity of the positive electrode active material may be reduced.

Further, the present invention provides a method of preparing thelithium cobalt oxide using the cobalt precursor, the method including:

(a) a process of preparing the cobalt precursor which is doped withdopants provided from a doping precursor by co-precipitation reaction ofa cobalt acid salt and the doping precursor; and

(b) a process of mixing the dopant-doped cobalt precursor and a lithiumprecursor, followed by heat treatment.

In other words, the lithium cobalt oxide may be prepared by reacting thedopant-doped cobalt precursor with the lithium precursor after dopingthe cobalt precursor with the dopants. Accordingly, in the lithiumcobalt oxide, process variables to be considered may be minimizedwithout competition between the dopants and the lithium ions for thecobalt position, and therefore, the average oxidation number of thedopants in the lithium cobalt oxide may be easily controlled within thedesired range.

In this case, the doping precursor may be mixed such that a content ofthe cobalt is in the range of 99 wt % to 99.8 wt %, and a total contentof the dopants is in the range of 0.2 wt % to 1 wt %, when the sum ofthe cobalt and the dopants is regarded as 100 wt %.

When the content of the dopants is too high out of the above range, thecontent of the cobalt in the lithium cobalt oxide may be decreased tolower the capacity of the lithium cobalt oxide.

Therefore, the doping precursor may be mixed such that the content ofthe cobalt is in the range of 99 wt % to 99.8 wt %, and the totalcontent of the dopants is in the range of 0.2 wt % to 1 wt %, when thesum of the cobalt and the dopants is regarded as 100 wt %, therebypreventing reduction in the capacity of the lithium cobalt oxideaccording to doping of the dopants.

On the contrary, when the content of the dopant is too low, it isdifficult to achieve the effect of improving structural stabilityaccording to doping of the dopants.

In a specific embodiment, the heat treatment of the process (b) may beperformed at 950° C. to 1100° C. for 8 hours to 15 hours.

When the heat treatment of the process (b) is performed at anexcessively low temperature or for a too short time out of the aboverange, the reaction between the cobalt and the lithium is not enough toform the stable lithium cobalt oxide.

On the contrary, when the heat treatment of the process (b) is performedat an excessively high temperature or for a too long time out of theabove range, the lithium cobalt oxide particle become too large, whichmay influence performances of the lithium cobalt oxide or may cause achange in physical, chemical properties.

In a specific embodiment, the cobalt acid salt may be cobaltoxyhydroxide (CoOOH).

Further, the lithium precursor may be one or more selected from thegroup consisting of Li₂CO₃, LiOH, LiNO₃, CH₃COOLi, and Li₂(COO)₂.

Meanwhile, the doping precursor may be one or more selected from thegroup consisting of a mixed metal of Mg and one or more selected fromthe group consisting of Al, Ti, Mn, Zr, Ba, B, Ca, Ta, Mo, Nb, W, Sr,and P, a metal oxide thereof, and a metal salt thereof.

However, the lithium precursor or the doping precursor is not limitedthereto, and the kind thereof is not limited as long as it may be usedto prepare lithium cobalt oxide capable of maintaining a stablestructure without deterioration of performances of the positiveelectrode active material.

Meanwhile, the cobalt precursor according to the present invention maybe a cobalt precursor for preparing lithium cobalt oxide of the layeredstructure which is included in the positive electrode active material,wherein the cobalt precursor is cobalt oxyhydroxide((Co_(x)Mg_(y)M′_(z))OOH) doped with, as dopants, magnesium (Mg) and M′different from the magnesium; and

the lithium cobalt oxide is represented by the following Formula 1;

the dopants have an average oxidation number of more than +2 and +2.5 orless in the lithium cobalt oxide; and

the lithium cobalt oxide may have a structure in which a ratio(IO3/IH1-3) of a peak intensity of O3 phase to a peak intensity of H1-3phase is more than 1 in the spectrum of X-ray diffraction (XRD) analysisusing Cu—Kα:

Li_(a)(Co_(x)Mg_(y)M′_(z))O₂   (1)

wherein a satisfies 0.95≤a≤1.05;

x, y, and z satisfy the following weight ratio conditions: a content ofx is in the range of 99 wt % to 99.8 wt % and a total content of y and zis in the range of 0.2 wt % to 1 wt %, when the sum of x, y, and z isregarded as 100 wt %; and

M′ is one or more selected from the group consisting of Al, Ti, Mn, Zr,Ba, B, Ca, Ta, Mo, Nb, W, Sr, and PO₄.

Therefore, the lithium cobalt oxide may maintain the stable crystalstructure of O3 phase even at a charging voltage of higher than 4.53 V,thereby preventing deterioration of operating efficiency and dischargerate and lifespan characteristics of a secondary battery and achievingexcellent performances.

Meanwhile, the present invention provides a secondary battery includinga positive electrode including the lithium cobalt oxide, a negativeelectrode, and an electrolyte. The kind of the secondary battery is notparticularly limited, but specific example thereof may include lithiumsecondary batteries having advantages of high energy density, dischargevoltage, output stability, etc., such as a lithium ion battery, alithium ion polymer battery, etc.

Generally, the lithium secondary battery consists of a positiveelectrode, a negative electrode, a separator, and a non-aqueouselectrolyte containing lithium salts.

The positive electrode may be fabricated by, for example, applying amixture of the positive electrode active material, a conductivematerial, and a binder onto a positive electrode collector, followed bydrying. If necessary, a filler may be further added to the mixture.

The conductive material is generally added in an amount of 1 wt % to 30wt % based on the total weight of the mixture including the positiveelectrode active material. The conductive material is not particularlylimited, as long as it has conductivity without causing chemical changesin the battery. Examples of the conductive material may include graphitesuch as natural or artificial graphite; carbon black such as carbonblack, acetylene black, Ketjen black, channel black, furnace black, lampblack, thermal black, etc.; conductive fibers such as carbon fibers,metallic fibers, etc.; metallic powders such as carbon fluoride,aluminum, nickel powder, etc.; conductive whiskers such as zinc oxide,potassium titanate, etc.; conductive metal oxides such as titaniumoxide, etc.; polyphenylene derivatives, etc.

The binder is a component that assists in bonding between the activematerial and the conductive material and bonding with respect to thecollector, and may be generally added in an amount of 1% by weight to30% by weight based on the total weight of the mixture including thepositive electrode active material. Examples of the binder may includepolyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose(CMC), starch, hydroxypropyl cellulose, regenerated cellulose,polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene,ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM,styrene-butadiene rubber, fluorine rubber, various copolymers, etc.

The filler is a component optionally used to inhibit expansion of thepositive electrode. The filler is not particularly limited, as long asit is a fibrous material without causing chemical changes in thecorresponding battery. For example, olefinic polymers such aspolyethylene, polypropylene, etc.; and fibrous materials such as glassfibers, carbon fibers, etc. may be used.

The negative electrode may be fabricated by applying a negativeelectrode active material onto a negative electrode collector, followedby drying. If necessary, the above-described components may be furtherincluded, optionally.

The negative electrode active material may include, for example, carbonsuch as non-graphitized carbon, graphitized carbon, etc.; metalcomposite oxides such as Li_(x)Fe₂O₃(O≤x≤1), Li_(x)WO₂(O≤x≤1),Sn_(x)Me_(1-x)Me′_(y)O_(z) (Me: Mn, Fe, Pb, Ge; Me′; Al, B, P, Si, GroupI, II, or III elements of the periodic table, halogen; 0≤x≤1; 1≤y≤3;1≤z≤8), etc.; lithium metal; lithium alloys; silicon-based alloys;tin-based alloys; metal oxides such as SnO, SnO₂, PbO, PbO₂, Pb₂O₃,Pb₃O₄, Sb₂O₃, Sb₂O₄, Sb₂O₅, GeO, GeO₂, Bi₂O₃, Bi₂O₄, and Bi₂O₅, etc.;conductive polymers such as polyacetylene, etc.; Li—Co—Ni-basedmaterials, etc.

The separator and separation film are interposed between the positiveelectrode and the negative electrode, and an insulating thin film havinghigh ion permeability and mechanical strength is used. The separatorgenerally has a pore diameter of 0.01 μm to 10 μm and a thickness of 5μm to 300 μm. As the separator, for example, a sheet or non-woven fabricmade of olefin polymer, such as polypropylene having chemical resistanceand hydrophobicity, etc.; or a glass fiber or polyethylene is used. Whena solid electrolyte such as a polymer, etc. is employed as theelectrolyte, the solid electrolyte may also serve as both the separatorand the electrolyte.

Further, in one specific embodiment, in order to improve safety of thebattery of high energy density, the separator and/or the separation filmmay be an organic/inorganic composite porous SRS (Safety-ReinforcingSeparators).

The SRS separator may be manufactured by applying an active layer,including inorganic particles and a binder polymer, onto apolyolefin-based separator substrate. In this case, the SRS separatorhas a pore structure which is included in the separator substrate aswell as a uniform pore structure which is formed by the interstitialvolume among inorganic particles as active layer ingredients.

Compared to use of a common separator, use of the organic/inorganiccomposite porous separator is advantageous in that increase of thebattery thickness according to swelling during a formation process maybe inhibited. In the case where a gellable polymer is used as a binderpolymer component when a liquid electrolyte is impregnated, theorganic/inorganic composite porous separator may also serve as anelectrolyte.

Further, since the organic/inorganic composite porous separator mayexhibit excellent adhesion property by controlling the contents ofinorganic particles and binder polymer which are active layer componentspresent in the separator, a battery assembly process may be easilyperformed.

The inorganic particles are not particularly limited, as long as theyare electrochemically stable. That is, the inorganic particles that maybe used in the present invention are not particularly limited, as longas the inorganic particles are not oxidized and/or reduced within anoperating voltage range (e.g., 0 to 5 V based on Li/Li⁺) of a battery towhich inorganic particles are applied. In particular, when inorganicparticles having ion transfer ability are used, it is possible toimprove ion conductivity in an electrochemical element, therebyimproving the performance of the battery. Accordingly, it is preferablethat ion conductivity of the inorganic particles is as high as possible.In the case of inorganic particles having high density, there is adifficulty in dispersing the inorganic particles at the time of coating,and there is a problem that the weight of the battery may increase. Forthese reasons, it is preferable that density of the inorganic particlesis as low as possible. Additionally, in the case of inorganic particleshaving high permittivity, a degree of dissociation of electrolyte salts,such as lithium salts, in a liquid electrolyte may increase, therebyimproving ion conductivity of the electrolyte.

The lithium salt-containing non-aqueous electrolyte is composed of apolar organic electrolyte and lithium salt. A non-aqueous liquidelectrolyte, an organic solid electrolyte, or an inorganic solidelectrolyte may be used as the electrolyte.

The non-aqueous liquid electrolyte may be, for example, a non-proticorganic solvent, such as N-methyl-2-pyrrolidone, propylene carbonate,ethylene carbonate, butylene carbonate, dimethyl carbonate, diethylcarbonate, gamma butyrolactone, 1,2-dimethoxy ethane, tetrahydroxyfranc, 2-methyl tetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane,formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane,methyl formate, methyl acetate, phosphoric acid triester, trimethoxymethane, dioxolane derivatives, sulfolane, methyl sulfolane,1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives,tetrahydrofuran derivatives, ether, methyl propionate, ethyl propionate,etc.

The organic solid electrolyte may include, for example, polyethylenederivatives, polyethylene oxide derivatives, polypropylene oxidederivatives, phosphoric acid ester polymer, polyagitation lysine,polyester sulfide, polyvinyl alcohol, polyvinylidene fluoride, a polymercontaining ionic dissociation groups, etc.

The inorganic solid electrolyte may include, for example, Li-basednitrides, halides, or sulfates such as Li₃N, LiI, Li₅NI₂, Li₃N—LiI—LiOH,LiSiO₄, LiSiO₄—LiI—LiOH, Li₂SiS₃, Li₄SiO₄, Li₄SiO₄—LiI—LiOH,Li₃PO₄—Li₂S—SiS₂, etc.

The lithium salts are substance that are readily dissolved in thenon-aqueous electrolyte, and may include, for example, LiCl, LiBr, LiI,LiClO₄, LiBF₄, LiB₁₀Cl₁₀, LiPF₆, LiCF₃SO₃, LiCF₃CO₂, LiAsF₆, LiSbF₆,LiAlCl₄, CH₃SO₃Li, CF₃SO₃Li, (CF₃SO₂)₂NLi, chloroboran lithium, loweraliphatic carboxylic acid lithium, lithium tetraphenyl borate, imides,etc.

In order to improve charge/discharge characteristics and flameretardancy, for example, pyridine, triethyl phosphite, triethanolamine,cyclic ether, ethylene diamine, n-glyme, hexaphosphoric triamide,nitrobenzene derivatives, sulfur, quinoneimine dyes, N-substitutedoxazolidinone, N,N-substituted imidazolidine, ethyleneglycoldialkylether, ammonium salts, pyrrol, 2-methoxy ethanol, aluminumtrichloride, etc. may be added to the non-aqueous electrolyte.Optionally, halogen-containing solvents such as carbon tetrachloride orethylene trifluoride may be further added in order to provide flameresistance, or carbon dioxide gas may be further added in order toenhance high-temperature retention properties.

Effect of the Invention

As described above, a cobalt precursor according to the presentinvention is composed of cobalt oxyhydroxide (CoOOH) which is dopedwith, as dopants, magnesium (Mg) and M′ different from the magnesium,and the dopants doped into lithium cobalt oxide of a positive electrodeactive material prepared using the cobalt precursor exhibit a particularaverage oxidation number, and as a result, a crystal lattice havingexcellent structural stability may be formed, oxidation of cobalt ionsconstituting the lithium cobalt oxide may be prevented to prevent areduction of ionic radius and an increase in structural stress, and anirreversible phase transition and a structural change of the lithiumcobalt oxide may be effectively prevented even at a charging voltage ofhigher than 4.53 V, thereby preventing deterioration of operatingefficiency and discharge rate and lifespan characteristics of asecondary battery including the positive electrode active material andimproving performances thereof.

BRIEF DESCRIPTION OF DRAWINGS

FIGS. 1A and 1B show graphs of capacity retention ratios according toExperimental Example 1 of the present invention;

FIGS. 2 and 3 show XRD graphs of peak intensities according toExperimental Example 2 of the present invention; and

FIG. 4 shows a graph of a discharge rate according to ExperimentalExample 3 of the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Hereinafter, the present invention will be described in more detail withreference to Examples. However, the scope of the present invention isnot intended to be limited by these Examples.

Preparation of Positive Electrode Active Material

EXAMPLE 1

Each of Mg(SO₄), Al(SO₄)₃, and Co(SO₄) was added to an aqueous solutionalong with NaOH and NH₄OH according to a stoichiometric ratio thereofsuch that Mg and Al were included in an amount of 3000 ppm and 2000 ppm,respectively, based on the total weight of Al lithium cobalt oxide, andco-precipitation was allowed to prepare a cobalt precursor (Co—Mg—Al)OOH(a total content of dopants: 0.5 wt %) doped with Mg and Al.

The cobalt precursor was mixed with Li₂CO₃ at a Li/M ratio of 1.02, andthen sintered in a furnace at 1050° C. for 10 hours to prepare a lithiumcobalt oxide Li_(1.02)(Co—Mg—Al)O₂ (a total content of dopants: 0.5 wt%) doped with Mg and Al at the cobalt position thereof.

EXAMPLE 2

A cobalt precursor (Co—Mg—Al)OOH (a total content of dopants: 0.2 wt %)doped with Mg and Al was prepared in the same manner as in Example 1,except that Mg and Al were included in an amount of 1000 ppm and 1000ppm, respectively, based on the total weight of lithium cobalt oxide inExample 1. This cobalt precursor was used to prepare a lithium cobaltoxide.

EXAMPLE 3

A cobalt precursor (Co—Mg—Al)OOH (a total content of dopants: 1 wt %)doped with Mg and Al was prepared in the same manner as in Example 1,except that Mg and Al were included in an amount of 4000 ppm and 6000ppm, respectively, based on the total weight of lithium cobalt oxide inExample 1. This cobalt precursor was used to prepare a lithium cobaltoxide.

COMPARATIVE EXAMPLE 1

A lithium cobalt oxide Li_(1.02)CoO₂ was prepared using CoOOH and LiOHin the same amounts as in Example 1, except that Mg and Al were notincluded.

COMPARATIVE EXAMPLE 2

200 g of the lithium cobalt oxide Li_(1.02)CoO₂ prepared in ComparativeExample 1 was dry-mixed with 0.995 g of MgO and 1.55 g of Al₂O₃ suchthat Mg and Al were included in an amount of 3000 ppm and 2000 ppm,respectively, based on the total weight of lithium cobalt oxide. Then,the mixture was sintered in a furnace at 500° C. for 5 hours to preparea lithium cobalt oxide coated with magnesium oxide and aluminum oxide onthe surface thereof.

COMPARATIVE EXAMPLE 3

0.995 g of MgO, 1.55 g of Al₂O₃, 200 g of CoOOH, and 79.5 g of Li₂CO₃were dry-mixed with each other such that Mg and Al were included in anamount of 3000 ppm and 2000 ppm, respectively, based on the total weightof lithium cobalt oxide. Then, the mixture was sintered in a furnace at1050° C. for 10 hours to prepare a lithium cobalt oxideLi_(1.02)(Co—Mg—Al)O₂ (a total content of dopants: 0.5 wt %) doped withMg and Al at the cobalt position thereof.

COMPARATIVE EXAMPLE 4

A lithium cobalt oxide Li_(1.02)(Co—Mg—Al)O₂ (a total content ofdopants: 0.13 wt %) was prepared in the same manner as in Example 1,except that Mg and Al were included in an amount of 500 ppm and 800 ppm,respectively, based on the total weight of lithium cobalt oxide.

Manufacture of Secondary Battery

Each of the positive electrode active materials prepared in Examples 1to 3, and Comparative Examples 1 to 4, a PVdF binder, and a naturalgraphite conductive material were mixed well at a weight ratio of 96:2:2(positive electrode active material:binder:conductive material) in NMP,and then applied to an Al foil having a thickness of 20 and dried at130° C. to manufacture each positive electrode. As a negative electrode,a lithium foil was used, an electrolyte containing 1M LiPF₆ in a solventof EC:DMC:DEC=1:2:1 was used to manufacture each coin-type half cell.

EXPERIMENTAL EXAMPLE 1

Analysis of Capacity Retention Ratio

From the coin-type half cells as manufactured above, the coin-type halfcells including each of the positive electrode active materials ofExamples 1 to 3 and Comparative Examples 1 to 4 were charged at 0.5 C toan upper voltage limit of 4.55 V at 25° C., and then discharged at 1.0 Cto a lower voltage limit of 3 V. This procedure was regarded as 1 cycle,and capacity retention ratios after 50 cycles were measured. The resultsof measuring the capacity retention ratios of Example 1 and ComparativeExamples 1 to 4 are shown in FIG. 1A, and the results of Examples 2 and3 are shown in FIG. 1B.

Referring to FIG. 1A, when Mg and Al were doped in an amount of 3000 ppmand 2000 ppmm, respectively as in Example 1, the coin-type half cellmanufactured using the positive electrode active material of Example 1showed a capacity retention ratio similar to the coin-type half cellsmanufactured using the positive electrode active materials ofComparative Examples 1 to 4, after less than about 50 cycles. However,over 50 cycles, Example 1 showed more excellent capacity retentionratio. Further, referring to FIG. 1B, in Examples 2 and 3, even thoughthe doping amounts of Mg and Al were controlled within the range of thepresent invention, excellent capacity retention ratio equivalent to thatof Example 1 was observed.

Accordingly, when the contents of the dopants are controlled in thepositive electrode active material according to the present invention,the average oxidation number of the dopants in the lithium cobalt oxidemay be controlled within the desired range, thereby achieving improvedlifespan characteristic at a high voltage of 4.5 V or more.

EXPERIMENTAL EXAMPLE 2

XRD Analysis

In order to examine changes in the crystal structures of the lithiumcobalt oxides of Example 1 and Comparative Examples 1, 3 and 4,coin-type half cells including the same were manufactured, and peakintensity was measured while increasing the upper limit voltage from4.53 V to 4.55 V at 0.01 V intervals. The XRD graphs (2-theta-scale)thus measured are shown in FIGS. 2 and 3.

Referring to FIGS. 2 and 3, the positive electrode active material ofExample 1 showed a peak in the range of 23 to 24 degree even at 4.55 V,and a peak intensity of (003) plane at 4.55 V was 70% or more of a peakintensity of (003) plane at 4.53 V. Even at the high voltage, there wasno phase transition of the lithium cobalt oxide or no collapse of thecrystal structure, indicating improvement of structural stability.However, the positive electrode active materials of Comparative Examples1, 3 and 4 showed remarkably low peak intensities of (003) plane at 4.55V, indicating that the phase transition of the lithium cobalt oxides orcollapse of the crystal structures occurred.

EXPERIMENTAL EXAMPLE 3

Discharge Rate Analysis

From the coin-type half cells as manufactured above, the coin-type halfcells including each of the positive electrode active materials ofExample 1 and Comparative Example 1 were initially charged at 0.5 C toan upper voltage limit of 4.55 V at 25° C., and then initiallydischarged at 1.0 C to a lower voltage limit of 3 V. Thereafter,discharge rates were measured and the results are shown in FIG. 4.

Referring to FIG. 4, when Mg and Al were doped in an amount of 3000 ppmand 2000 ppmm, respectively as in Example 1, the crystal structure ofthe lithium cobalt oxide was stably maintained, and the discharge ratewas mostly constant, and therefore, a plateau, in which the voltagemaintains constant, was not observed. However, Comparative Example 1including no Mg and Al showed a rapid change in the discharge rate dueto phase transition of the lithium cobalt oxide, and therefore, aplateau, in which the voltage maintains constant, was observed.

Although the present invention has been described in connection with theexemplary embodiments of the present invention, it will be apparent tothose skilled in the art to which the present invention pertains thatvarious modifications and changes may be made thereto without departingfrom the scope of the invention.

1. A cobalt precursor for preparing a lithium cobalt oxide of a layeredstructure which is included in a positive electrode active material,wherein the cobalt precursor is cobalt oxyhydroxide((Co_(x)Mg_(y)M′_(z))OOH) wherein (x, y, and z satisfy the followingweight ratio conditions: a content of x is in the range of 99 wt % to99.8 wt % and a total content of y and z is in the range of 0.2 wt % to1 wt %, when the sum of x, y, and z is regarded as 100 wt %; M′ is oneor more selected from the group consisting of Al, Ti, Mn, Zr, Ba, B, Ca,Ta, Mo, Nb, W, Sr and PO₄ wherein the cobalt precursor is doped with, asdopants, magnesium (Mg) and M′.
 2. A lithium cobalt oxide having alayered structure for a positive electrode active material, wherein thelithium cobalt oxide is represented by the following Formula 1, anddoped with, as dopants, magnesium (Mg) and M′; and the dopants have anaverage oxidation number of more than +2 to +2.5 or less in the lithiumcobalt oxide:Li_(a)(Co_(x)Mg_(y)M′_(z))O₂   (1) wherein a satisfies 0.95≤a≤1.05; x,y, and z satisfy the following weight ratio conditions: a content of xis in the range of 99 wt % to 99.8 wt % and a total content of y and zis in the range of 0.2 wt % to 1 wt %, when the sum of x, y, and z isregarded as 100 wt %; and M′ is one or more selected from the groupconsisting of Al, Ti, Mn, Zr, Ba, B, Ca, Ta, Mo, Nb, W, Sr, and PO₄. 3.The lithium cobalt oxide of claim 2, wherein the lithium cobalt oxidemaintains a crystal structure in a charging range of more than 4.5 V and4.8 V or less.
 4. The lithium cobalt oxide of claim 3, wherein thecrystal structure is O3 phase.
 5. The lithium cobalt oxide of claim 2,wherein the lithium cobalt oxide has no plateau at 4.55 V of initialcharge/discharge profiles.
 6. The lithium cobalt oxide of claim 2,wherein the positive electrode active material is in the form ofparticles, and the surface of the particle is coated with Al₂O₃.
 7. Thelithium cobalt oxide of claim 6, wherein the Al₂O₃ is applied at athickness of 0.2% to 5%, based on a diameter of the positive electrodeactive material particle.
 8. A method of preparing a lithium cobaltoxide using the cobalt precursor, the method comprising: (a) preparingthe cobalt precursor of claim 1 which is doped with dopants providedfrom a doping precursor by co-precipitation reaction of a cobalt acidsalt and the doping precursor; and (b) mixing the dopant-doped cobaltprecursor and a lithium precursor to form a mixture; (c) heattreatmenting the mixture.
 9. The method of claim 8, wherein the dopingprecursor is mixed such that a content of the cobalt is in the range of99 wt % to 99.8 wt %, and a total content of the dopants is in the rangeof 0.2 wt % to 1 wt %, when the sum of the cobalt and the dopants isregarded as 100 wt %.
 10. The method of claim 8, wherein the heattreatmenting is performed at 950° C. to 1100° C. for 8 hours to 15hours.
 11. The method of claim 8, wherein the cobalt acid salt is cobaltoxyhydroxide (CoOOH).
 12. The method of claim 8, wherein the lithiumprecursor is one or more selected from the group consisting of Li₂CO₃,LiOH, LiNO₃, CH₃COOLi, and Li₂(COO)₂.
 13. The method of claim 8, whereinthe doping precursor includes: one or more selected from the groupconsisting of a mixed metal of Mg, and one or more selected from thegroup consisting of Al, Ti, Mn, Zr, Ba, B, Ca, Ta, Mo, Nb, W, Sr, and P,a metal oxide thereof, and a metal salt thereof.
 14. The lithium cobaltoxide of claim 2, wherein the lithium cobalt oxide has a structure inwhich a ratio (IO3/IH1-3) of a peak intensity of O3 phase to a peakintensity of H1-3 phase is more than 1 in the spectrum of X-raydiffraction (XRD) analysis using Cu—Kα:Li_(a)(Co_(x)Mg_(y)M′_(z))O₂   (1) wherein a satisfies 0.95≤a≤1.05; x,y, and z satisfy the following weight ratio conditions: a content of xis in the range of 99 wt % to 99.8 wt % and a total content of y and zis in the range of 0.2 wt % to 1 wt %, when the sum of x, y, and z isregarded as 100 wt %; and M′ is one or more selected from the groupconsisting of Al, Ti, Mn, Zr, Ba, B, Ca, Ta, Mo, Nb, W, Sr, and PO₄.